Hair treatment method

ABSTRACT

The present invention provides a method of treating hair, the method comprising the following steps: applying a composition to the hair, the composition comprising one or more active ingredients selected from the following: hair conditioning agents; reducing agents; organic or inorganic bases; hair dyes; abrasive solid particles; and moisturizing agents; and combing the hair using a motor-driven combing device ( 10 ) comprising spikes that are driven in an oscillating motion.

The present invention relates to methods, devices and kits for treating hair.

Tools for cleaning or massaging the hair are known from U.S. Pat. No. 6,283,930 B, JP 2002-363039 A, JP 2005-046190 A, CN 2010 44658 Y and JP 11070019 A.

European application EP 1 825 842 A1 describes a massage device for massaging the scalp when washing the hair, for example, and envisages using it at the same time as shampoo is used.

The application US 2009/0182249 A1 discloses a device for massaging the scalp, comprising a reservoir that can accommodate a liquid such as a shampoo or a lotion for stimulating hair growth. Various devices for massaging the scalp are also disclosed in the publications EP 1 972 317 A1, EP 1 964 537 A1, and EP 2 080 500 A1.

There is a need for a method and for a treatment kit that can be used to improve the efficacy of the active ingredients in hair treatments.

In first exemplary embodiments the invention provides a cosmetic hair treatment method comprising the steps consisting in:

-   -   applying a composition to the hair, the composition comprising         one or more active ingredients selected from the following:         -   hair conditioning agents;         -   reducing agents;         -   organic or inorganic bases;         -   hair dyes;         -   abrasive solid particles; and         -   moisturizing agents; and     -   combing the hair using a motor-driven combing device comprising         spikes that are driven in an oscillating motion.

Hair combing using a motor-driven device can be carried out after applying the composition of the invention to the hair, preferably in the presence of the composition on the hair.

Hair combing using a motor-driven device may be carried out before applying the composition of the invention to the hair, in particular after wetting the hair or after applying a composition not including any active ingredient of the invention. By way of example, combing may be carried out less than 60 minutes before applying the composition containing the active ingredient of the invention.

Applying the method to frizzy or curly hair in association with the composition containing the active ingredient results in a very distinct reduction in volume and density, in better disentangling, and in a smoother feel.

Preferably, the combing device is characterized in that it includes a flexible diaphragm carrying spikes and a drive mechanism that enables the diaphragm to deform periodically in order to generate movement of the spikes.

The drive mechanism preferably includes a connecting rod that is driven in oscillating motion, which connecting rod is connected at one end to a member that is driven in rotation by an electric motor and is connected directly or indirectly at its other end to the flexible diaphragm, in particular in a central region thereof.

The frequency of oscillation of the diaphragm preferably lies in the range 0.5 Hz [Hertz] to 200 Hz, better preferably in the range 1 Hz to 20 Hz, the limits of the ranges being included in the ranges.

The envelope surface defined by the free ends of the spikes may be a surface that is concave towards the scalp, with a radius of curvature that varies as a function of the deformations of the diaphragm.

During oscillation of the diaphragm, at least some of the spikes rub against the hair. Performance is improved by rubbing these spikes on the hair in combination with using the composition. The invention enables a superior effect to be achieved than that obtained manually. The travel axis of the flexible diaphragm, i.e. the axis of the oscillating movement, may be substantially perpendicular to the scalp during combing, at least while combing the base of hair.

Preferably, the spikes are made out of a thermoplastic material.

In other exemplary embodiments the invention provides a cosmetic hair treatment method comprising the steps consisting in:

-   -   applying a composition to the hair, the composition comprising         one or more active ingredients selected from the following:         -   hair conditioning agents;         -   reducing agents;         -   organic or inorganic bases;         -   hair dyes;         -   abrasive solid particles; and         -   moisturizing agents; and     -   combing the hair for a period of 1 minute to 5 minutes using a         motor-driven combing device comprising spikes that are driven in         an oscillating motion.

In other exemplary embodiments the invention also provides a motor-driven combing device for carrying out one of the above methods.

The invention also provides a motor-driven combing device comprising: a flexible diaphragm carrying spikes adapted to come into contact with the hair; a drive mechanism enabling the diaphragm to deform periodically in order to generate movement of the spikes in contact with the hair; and a reservoir containing a composition for application, in the form of a pre-filled removable cartridge.

Active Ingredients

The composition of the invention applied to the hair may contain at least one of the following active ingredients.

The active ingredient or ingredients may be applied alone or in combination with other ingredients. When applied in combination, the active ingredient may represent up to 50% by weight of the total composition weight, preferably up to 20% by weight of the total composition weight.

The active ingredient or ingredients may represent more than 0.001%, preferably more than 0.1%, more preferably more than 0.2%; and more particularly more than 0.5% by weight relative to the total composition weight.

Hair Dyes

The term “hair dye” as used in the present invention means synthetic direct dyes, natural dyes, and precursors of oxidation dyes.

These hair dyes may be non-ionic or ionic, in particular cationic or anionic.

The precursor or precursors of the oxidation dyes present in the composition of the present invention may be selected from oxidation bases and coupling agents in conventional use in oxidation dyeing.

The oxidation base or bases may be selected from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, bis-para-aminophenols, ortho-aminophenols, ortho-phenylenediamines, heterocyclic bases, and their addition salts.

Examples of para-phenylenediamines that may be mentioned are para-phenylenediamine, para-toluenediamine, 2-chloro para-phenylenediamine, 2,3-dimethyl para-phenylenediamine, 2,6-dimethyl para-phenylenediamine, 2,6-diethyl para-phenylenediamine, 2,5-dimethyl para-phenylenediamine, N,N-dimethyl para-phenylenediamine, N,N-diethyl para-phenylenediamine, N,N-dipropyl para-phenylenediamine, 4-amino N,N-diethyl 3-methyl aniline, N,N-bis-(β-hydroxyethyl) para-phenylenediamine, 4-N,N-bis-(β-hydroxyethyl)amino 2-methyl aniline, 4-N,N-bis-(β-hydroxyethyl)amino 2-chloro aniline, 2-β-hydroxyethyl para-phenylenediamine, 2-fluoro para-phenylenediamine, 2-isopropyl para-phenylenediamine, N-(β-hydroxypropyl) para-phenylenediamine, 2-hydroxymethyl para-phenylenediamine, N,N-dimethyl 3-methyl para-phenylenediamine, N,N-(ethyl, β-hydroxyethyl) para-phenylenediamine, N-(β,γ-dihydroxypropyl) para-phenylenediamine, N-(4′-aminophenyl) para-phenylenediamine, N-phenyl para-phenylenediamine, 2-β-hydroxyethyloxy para-phenylenediamine, 2-β-acetylaminoethyloxy para-phenylenediamine, N-(β-methoxyethyl) para-phenylene-diamine, 4-aminophenyl pyrrolidine, 2-thienyl para-phenylenediamine, 2-β-hydroxyethylamino 5-amino toluene, 3-hydroxy 1-(4′-aminophenyl)pyrrolidine, and their addition salts.

Particularly preferred examples of the above-mentioned para-phenylenediamines are para-phenylenediamine, para-toluenediamine, 2-isopropyl para-phenylenediamine, 2-β-hydroxyethyl para-phenylenediamine, 2-β-hydroxyethyloxy para-phenylenediamine, 2,6-dimethyl para-phenylenediamine, 2,6-diethyl para-phenylenediamine, 2,3-dimethyl para-phenylenediamine, N,N-bis-(β-hydroxyethyl) para-phenylenediamine, 2-chloro para-phenylenediamine, 2-β-acetylaminoethyloxy para-phenylenediamine, and their addition salts.

Examples of bis-phenylalkylenediamines that may be mentioned are N,N′-bis-(β-hydroxyethyl) N,N′-bis-(4′-aminophenyl) 1,3-diamino propanol, N,N′-bis-(β-hydroxyethyl) N,N′-bis-(4′-aminophenyl) ethylenediamine, N,N′-bis-(4-aminophenyl)tetramethylenediamine, N,N′-bis-(β-hydroxyethyl) N,N′-bis-(4-aminophenyl)tetramethylenediamine, N,N′-bis-(4-methyl-aminophenyl)tetramethylenediamine, N,N′-bis-(ethyl) N,N′-bis-(4′-amino, 3′-methylphenyl) ethylenediamine, 1,8-bis-(2,5-diamino phenoxy)-3,6-dioxaoctane, and their addition salts.

More particular examples of para-aminophenols that may be mentioned are para-aminophenol, 4-amino 3-methyl phenol, 4-amino 3-fluoro phenol, 4-amino 3-hydroxymethyl phenol, 4-amino 2-methyl phenol, 4-amino 2-hydroxymethyl phenol, 4-amino 2-methoxymethyl phenol, 4-amino 2-aminomethyl phenol, 4-amino 2-(β-hydroxyethyl aminomethyl) phenol, 4-amino 2-fluoro phenol, and their addition salts.

Examples of ortho-aminophenols that may be mentioned are 2-aminophenol, 2-amino 5-methyl phenol, 2-amino 6-methyl phenol, 5-acetamido 2-aminophenol, and their addition salts.

Examples of heterocyclic bases that may be mentioned are pyridine derivatives, pyrimidine derivatives and pyrazolic derivatives.

Examples of pyridine derivatives that may be mentioned are the compounds described, for example, in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diamino pyridine, 2-(4-methoxyphenyl)amino 3-amino pyridine, 2,3-diamino 6-methoxy pyridine, 2-(β-methoxyethyl)amino 3-amino 6-methoxy pyridine, 3,4-diamino pyridine, and their addition salts.

Other pyridinic oxidation bases that may be used in the present invention are 3-amino pyrazolo-[1,5-a]-pyridine oxidation bases, or their addition salts, as described in patent application FR 2 801 308, for example. Examples that may be mentioned are pyrazolo[1,5-a]pyridin-3-ylamine; 2-acetylamino pyrazolo-[1,5-a]pyridin-3-ylamine; 2-morpholin-4-yl-pyrazolo[1,5-a]pyridin-3-ylamine; 3-amino-pyrazolo[1,5-a]pyridin-2-carboxylic acid; 2-methoxy-pyrazolo[1,5-a]pyridine-3-ylamino; (3-amino-pyrazolo[1,5-a]pyridine-7-yl)-methanol; 2-(3-amino-pyrazolo[1,5-a]pyridine-5-yl)-ethanol; 2-(3-amino-pyrazolo[1,5-a]pyridine-7-yl)-ethanol; (3-amino-pyrazolo[1,5-a]pyridine-2-yl)-methanol; 3,6-diamino-pyrazolo[1,5-a]pyridine; 3,4-diamino-pyrazolo[1,5-a]pyridine; pyrazolo[1,5-a]pyridine-3,7-diamine; 7-morpholin-4-yl-pyrazolo[1,5-a]pyridin-3-ylamine; pyrazolo[1,5-a]pyridine-3,5-diamine; 5-morpholin-4-yl-pyrazolo[1,5-a]pyridin-3-ylamine; 2-[(3-amino-pyrazolo[1,5-a]pyridin-5-yl)-(2-hydroxyethyl)-amino]-ethanol; 2-[(3-amino-pyrazolo[1,5-a]pyridin-7-yl)-(2-hydroxyethyl)-amino]-ethanol; 3-amino-pyrazolo[1,5-a]pyridine-5-ol; 3-amino-pyrazolo[1,5-a]pyridine-4-ol; 3-amino-pyrazolo[1,5-a]pyridine-6-ol; 3-amino-pyrazolo[1,5-a]pyridine-7-ol; as well as their addition salts.

Examples of pyrimidine derivatives that may be mentioned are the compounds described, for example, in patents DE 23 59 399; JP 88-169571; JP 05-63124; EP 0 770 375 or patent application WO 96/15765 such as 2,4,5,6-tetra-aminopyrimidine, 4-hydroxy 2,5,6-triaminopyrimidine, 2-hydroxy 4,5,6-triaminopyrimidine, 2,4-dihydroxy 5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and pyrazolo-pyrimidine derivatives such as those mentioned in patent application FR-A-2 750 048; in which some that may be mentioned are pyrazolo-[1,5-a]-pyrimidine-3,7-diamine; 2,5-dimethyl pyrazolo-[1,5-a]-pyrimidine-3,7-diamine; pyrazolo-[1,5-a]-pyrimidine-3,5-diamine; 2,7-dimethyl pyrazolo-[1,5-a]-pyrimidine-3,5-diamine; 3-amino pyrazolo-[1,5-a]-pyrimidin-7-ol; 3-amino pyrazolo-[1,5-a]-pyrimidin-5-ol; 2-(3-amino pyrazolo-[1,5-a]-pyrimidin-7-ylamino)-ethanol, 2-(7-amino pyrazolo-[1,5-a]-pyrimidin-3-ylamino)-ethanol, 2-[(3-amino-pyrazolo[1,5-a]pyrimidin-7-yl)-(2-hydroxy-ethyl)-amino]-ethanol, 2-[(7-amino-pyrazolo[1,5-a]pyrimidin-3-yl)-(2-hydroxy-ethyl)-amino]-ethanol, 5,6-dimethyl pyrazolo-[1,5-a]-pyrimidine-3,7-diamine, 2,6-dimethyl pyrazolo-[1,5-a]-pyrimidine-3,7-diamine, 2,5,N7,N7-tetramethyl pyrazolo-[1,5-a]-pyrimidine-3,7-diamine, 3-amino-5-methyl-7-imidazolylpropylamino pyrazolo-[1,5-a]-pyrimidine, and their addition salts, and their tautomeric forms when a tautomeric equilibrium exists.

Examples of pyrazolic derivatives that may be mentioned are the compounds described in patents DE 38 43 892, DE 41 33 957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988, such as 4,5-diamino 1-(β-hydroxyethyl) pyrazole, 4,5-diamino 1-methyl pyrazole, 3,4-diamino pyrazole, 4,5-diamino 1-(4′-chlorobenzyl) pyrazole, 4,5-diamino 1,3-dimethyl pyrazole, 4,5-diamino 3-methyl 1-phenyl pyrazole, 4,5-diamino 1-methyl 3-phenyl pyrazole, 4-amino 1,3-dimethyl 5-hydrazino pyrazole, 1-benzyl 4,5-diamino 3-methyl pyrazole, 4,5-diamino 3-tert-butyl 1-methyl pyrazole, 4,5-diamino 1-tert-butyl 3-methyl pyrazole, 4,5-diamino 1-(β-hydroxyethyl) 3-methyl pyrazole, 4,5-diamino 1-ethyl 3-methyl pyrazole, 4,5-diamino 1-ethyl 3-(4′-methoxyphenyl) pyrazole, 4,5-diamino 1-ethyl 3-hydroxymethyl pyrazole, 4,5-diamino 3-hydroxymethyl 1-methyl pyrazole, 4,5-diamino 3-hydroxymethyl 1-isopropyl pyrazole, 4,5-diamino 3-methyl 1-isopropyl pyrazole, 4-amino 5-(2′-aminoethyl)amino 1,3-dimethyl pyrazole, 3,4,5-triamino pyrazole, 1-methyl 3,4,5-triamino pyrazole, 3,5-diamino 1-methyl 4-methylamino pyrazole, 3,5-diamino 4-(β-hydroxyethyl)amino 1-methyl pyrazole, 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, and their addition salts.

The coupling agent or agents present in the composition of the present invention may be selected from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic coupling agents, heterocyclic coupling agents, and their addition salts.

Examples that may be mentioned are 3-aminophenol, 2-methyl 5-aminophenol, 2-methyl 5-(β-hydroxyethylamino) phenol, 2-chloro 6-methyl 3-aminophenol, 1,3-dihydroxy benzene, 1,3-dihydroxy 2-methyl benzene, 4-chloro 1,3-dihydroxy benzene, 2,4-diamino 1-(β-hydroxyethyloxy) benzene, 2-amino 4-(β-hydroxyethylamino) 1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis-(2,4-diaminophenoxy) propane, 3-ureido aniline, 3-ureido 1-dimethylaminobenzene, sesamol, 1-β-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol, 2-methyl-1-naphthol, 6-hydroxy indole, 4-hydroxy indole, 4-hydroxy N-methyl indole, 2-amino-3-hydroxy pyridine, 6-hydroxy benzomorpholine, 3,5-diamino-2,6-dimethoxy pyridine, 1-N-(β-hydroxyethyl)amino-3,4-methylene dioxybenzene, 2,6-bis-(β-hydroxyethylamino) toluene, and their addition salts.

In general, addition salts of oxidation bases and coupling agents that may be used in the context of the invention are in particular selected from addition salts with an acid such as hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, (C₁-C₄)alkyl sulfonates, and in particular methylsulfonates, tosylates, benzenesulfonates, phosphates, and acetates, and addition salts with a base such as sodium hydroxide, potassium hydroxide, ammonia, amines, or alkanolamines.

The term “natural dyes” means any dye or dye precursor that occurs naturally and that is produced either by extraction (and possibly purification) from a plant matrix, or by chemical synthesis.

In contrast, the term “synthetic dyes” means any dye that does not occur naturally.

Examples of suitable synthetic direct dyes that may be mentioned are azo direct dyes; methine dyes; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri-(hetero)aryl methane dyes; used alone or as a mixture.

More particularly, azo dyes include an —N═N— function in which both nitrogen atoms are not simultaneously engaged in a cycle. However, it is also possible for one of the two nitrogen atoms of the —N═N— concatenation to be engaged in a cycle.

Dyes of the methine family are more particularly compounds comprising at least one concatenation selected from >C═C< and —N═C< in which both atoms are not simultaneously engaged in one cycle. However, it should be pointed out that one of the atoms of the concatenations, nitrogen or carbon, may be engaged in a cycle. More particularly, dyes of this family derive from compounds of the true methane type (comprising one or more of the above-mentioned —C═C— concatenations); of the azomethine type (including at least one or more —C═N— concatenations) with, for example, azacarbocyanins and their isomers, or diazacarbocyanins and their isomers, tetraazacarbocyanins; of the mono- and di-arylmethane type; indoamines (or diphenylamines); indophenols; indoanilines.

Examples of dyes of the carbonyl family that may be mentioned are dyes selected from acridone, benzoquinone, anthraquinone, naphthoquinone, benzanthrone, anthranthrone, pyranthrone, pyrazolanthrone, pyrimidinoanthrone, flavanthrone, idanthrone, flavone, (iso)violanthrone, isoindolinone, benzimidazolone, isoquinolinone, anthrapyridone, pyrazoloquinazolone, perinone, quinacridone, quinophthalone, indigoid, thioindigo, naphthalimide, anthrapyrimidine, diketopyrrolopyrrole, and coumarin.

Particular examples of dyes of the azine family that may be mentioned are azine, xanthene, thioxanthene, fluorindine, acridine, (di)oxazine, (di)thiazine, and pyronine.

More particular nitro (hetero)aromatic dyes are nitrobenzene direct dyes or nitropyridine dyes.

Regarding porphyrin or phthalocyanin dyes, it is possible to use cationic or non-cationic compounds, optionally including one or more metals or metallic ions such as alkali and alkaline-earth metals, zinc, or silicon, for example.

Particularly suitable examples of direct dyes that may be mentioned are nitrated dyes of the benzene series; azo direct dyes; methine dyes; azomethine dyes, more particularly with diazacarbocyanins and their isomers and tetraazacarbocyanins (tetraazapentamethines); quinone direct dyes and in particular anthraquinone, naphthoquinone or benzoquinone dyes; azine direct dyes; xanthene dyes; triarylmethane dyes; indoamine dyes; indigoid dyes; and phthalocyanins and porphyrins; used alone or as a mixture.

Preferably, the direct dyes are selected from nitro dyes of the benzene series; azo dyes; azomethines with diazacarbocyanins and their isomers, tetraazacarbocyanins (tetraazapentamethines); anthraquinone direct dyes; and triarylmethane direct dyes; used alone or as a mixture.

Still more preferably, said direct dyes are selected from nitro dyes of the benzene series; azo direct dyes; azomethines with diazacarbocyanins and their isomers, and tetraazacarbocyanins (tetraazapentamethines); alone or as a mixture.

Non-limiting examples of nitrobenzene direct dyes that may be used in accordance with the invention that may be mentioned are the following compounds:

-   1,4-diamino-2-nitrobenzene; -   1-amino-2 nitro-4-β-hydroxyethylaminobenzene; -   1-amino-2 nitro-4-bis(β-hydroxyethyl)-aminobenzene; -   1,4-bis(β-hydroxyethylamino)-2-nitrobenzene; -   1-β-hydroxyethylamino-2-nitro-4-bis-(β-hydroxyethylamino)-benzene; -   1-β-hydroxyethylamino-2-nitro-4-aminobenzene; -   1-β-hydroxyethylamino-2-nitro-4-(ethyl)(β-hydroxyethyl)-aminobenzene; -   1-amino-3-methyl-4-β-hydroxyethylamino-6-nitrobenzene; -   1-amino-2-nitro-4-β-hydroxyethylamino-5-chlorobenzene; -   1,2-diamino-4-nitrobenzene; -   1-amino-2-β-hydroxyethylamino-5-nitrobenzene; -   1,2-bis-(β-hydroxyethylamino)-4-nitrobenzene; -   1-amino-2-tris-(hydroxymethyl)-methylamino-5-nitrobenzene; -   1-hydroxy-2-amino-5-nitrobenzene; -   1-hydroxy-2-amino-4-nitrobenzene; -   1-hydroxy-3-nitro-4-aminobenzene; -   1-hydroxy-2-amino-4,6-dinitrobenzene; -   1-β-hydroxyethyloxy-2-β-hydroxyethylamino-5-nitrobenzene; -   1-methoxy-2-β-hydroxyethylamino-5-nitrobenzene; -   1-β-hydroxyethyloxy-3-methylamino-4-nitrobenzene; -   1-β□γ-dihydroxypropyloxy-3-methylamino-4-nitrobenzene; -   1-β-hydroxyethylamino-4-β,γ-dihydroxypropyloxy-2-nitrobenzene; -   1-β□γ-dihydroxypropylamino-4-trifluoromethyl-2-nitrobenzene; -   1-β-hydroxyethylamino-4-trifluoromethyl-2-nitrobenzene; -   1-β-hydroxyethylamino-3-methyl-2-nitrobenzene; -   1-β-aminoethylamino-5-methoxy-2-nitrobenzene; -   1-hydroxy-2-chloro-6-ethylamino-4-nitrobenzene; -   1-hydroxy-2-chloro-6-amino-4-nitrobenzene; -   1-hydroxy-6-bis-(β-hydroxyethyl)-amino-3-nitrobenzene; -   1-β-hydroxyethylamino-2-nitrobenzene; and -   1-hydroxy-4-β-hydroxyethylamino-3-nitrobenzene.

Examples of azo, azomethine, methine direct dyes that may be used in accordance with the invention and that may be mentioned are the cationic dyes described in patent applications WO 95/15144, WO 95/01772, and EP 7 149 54; FR 2 189 006, FR 2 285 851, FR 2 140 205, EP 1 378 544, and EP 1 674 073.

As an example, the synthetic direct dye or dyes may be selected from cationic monochromophoric direct dyes of the azo; methine; azomethine type with diazacarbocyanins and their isomers, tetraazacarbocyanins; and anthraquinones; used alone or as a mixture.

Thus, cationic direct dyes with the following formulae may in particular be mentioned:

in which:

-   -   D represents a nitrogen atom or the group —CH;     -   R₁ and R₂, which may be identical or different, represent a         hydrogen atom; a C₁-C₄ alkyl radical possibly substituted with a         —CN, —OH or —NH₂ radical or form a heterocycle, optionally         oxygen-containing or nitrogen-containing, with a carbon atom of         the benzene ring, possibly substituted with one or more C₁-C₄         alkyl radicals; or a 4′-aminophenyl radical;     -   R₃ and R′₃, which may be identical or different, represent a         hydrogen atom or halogen atom selected from chlorine, bromine,         iodine and fluorine, or a cyano, C₁-C₄ alkyl, C₁-C₄ alkoxy, or         acetyloxy radical;     -   X− represents an anion, preferably selected from the chloride,         methyl sulfate, and acetate;     -   A represents a group selected from the following structures:

in which R₄ represents a C₁-C₄ alkyl radical, possibly substituted with a hydroxyl radical;

in which:

-   -   R₅ represents a hydrogen atom, a C₁-C₄ alkoxy radical, a halogen         atom such as bromine, chlorine, iodine, or fluorine;     -   R₆ represents a hydrogen atom, a C₁-C₄ alkyl radical or forms,         with a carbon atom of the benzene ring, a heterocycle that         optionally contains oxygen and/or is substituted with one or         more C₁-C₄ alkyl groups;     -   R₇ represents a hydrogen atom or halogen atom such as bromine,         chlorine, iodine, or fluorine;     -   D₁ and D₂, which may be identical or different, represent a         nitrogen atom or the group —CH;     -   m=0 or 1;     -   X⁻ represents a cosmetically acceptable anion preferably         selected from chloride, methyl sulfate and acetate;     -   E represents a group selected from the following structures:

in which R′ represents a C₁-C₄ alkyl radical;

-   -   when m=0 and D₁ represents a nitrogen atom, then E may also         designate a group with the following structure:

in which R′ represents a C₁-C₄ alkyl radical.

More particular examples of the above-mentioned compounds are as follows:

X⁻ representing a cosmetically acceptable anion or mixture of anions.

Other dyes that may be used in accordance with the invention that may also be mentioned from azo direct dyes include the following dyes, described in the COLOR INDEX INTERNATIONAL 3rd edition:

-   -   Disperse Red 17;     -   Disperse Red 13;     -   Basic Red 22;     -   Basic Red 76;     -   Basic Yellow 57;     -   Basic Brown 16;     -   Basic Brown 17;     -   Disperse Green 9;     -   Disperse Black 9;     -   Solvent Black 3;     -   Disperse Blue 148;     -   Disperse Violet 63; and     -   Solvent Orange 7.         1-(4′-aminodiphenylazo)-2-methyl-4         bis-(β-hydroxyethyl)aminobenzene (INCI name: HC Yellow 7) may         also be mentioned.

Examples of direct quinone dyes that may be mentioned are the following dyes:

-   -   Disperse Red 15;     -   Solvent Violet 13;     -   Solvent Blue 14;     -   Disperse Violet 1;     -   Disperse Violet 4;     -   Disperse Blue 1;     -   Disperse Violet 8;     -   Disperse Blue 3;     -   Disperse Red 11;     -   Disperse Blue 7;     -   Disperse Blue 14;     -   Basic Blue 22;     -   Disperse Violet 15;     -   Disperse Blue 377;     -   Disperse Blue 60; and     -   Basic Blue 99;         as well as the following compounds:

-   1-N-methylmorpholiniumpropylamino-4-hydroxyanthraquinone;

-   1-aminopropylamino-4-methylaminoanthraquinone;

-   1-aminopropylaminoanthraquinone;

-   5-β-hydroxyethyl-1,4-diaminoanthraquinone;

-   2-aminoethylaminoanthraquinone; and

-   1,4-bis-(βγ-dihydroxypropylamino)-anthraquinone.

The coumarin Disperse Yellow 82 may also be mentioned.

Examples of azine dyes that may be mentioned are the following compounds:

-   -   Basic Blue 17;     -   Basic Red 2; and     -   Solvent Orange 15.

Examples of triarylmethane dyes that may be used in accordance with the invention and that may be mentioned are the following compounds:

-   -   Basic Green 1;     -   Basic Violet 3;     -   Basic Violet 14;     -   Basic Blue 7; and     -   Basic Blue 26.

Examples of indoamine dyes that may be used in accordance with the invention and that may be mentioned are the following compounds:

-   2-β-hydroxyethylamino-5-[bis-(β-4′-hydroxyethyl)amino]anilino-1,4-benzoquinone; -   2-β-hydroxyethylamino-5-(2′-methoxy-4′-amino)anilino-1,4-benzoquinone; -   3-N(2′-chloro-4′-hydroxy)phenyl-acetylamino-6-methoxy-1,4-benzoquinone     imine; -   3-N(3′-chloro-4′-methylamino)phenyl-ureido-6-methyl-1,4-benzoquinone     imine; and -   3-[4′-N-(ethylcarbamylmethyl)-amino]-phenyl-ureido-6-methyl-1,4-benzoquinone     imine.

Preferably, the direct cationic dyes are selected from direct dyes of the following types: azo; methine; azomethine with diazacarbocyanins and their isomers, tetraazacarbocyanins (tetraazapentamethines); anthraquinone; used alone or as a mixture.

Examples of direct anionic dyes that may in particular be mentioned are those described in the COLOR INDEX INTERNATIONAL 3rd edition listed under ACID and in particular:

-   -   Disperse Red 17;     -   Acid Yellow 9;     -   Acid Black 1;     -   Acid Yellow 36;     -   Acid Orange 7;     -   Acid Red 33;     -   Acid Red 35;     -   Acid Yellow 23;     -   Acid Orange 24;     -   Acid Violet 43;     -   Acid Blue 62;     -   Acid Blue 9;     -   Acid Violet 49; and     -   Acid Blue 7.

Particular natural dye or dyes that may be used to carry out the invention are preferably selected from lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, laccaic acid, purpurogallin, anthragallol, protocatechaldehyde, indigo, isatin, curcumin, spinusolin, chlorophylls, chlorophyllins, orceins, hematein, hematoxylin, brazilin, brazilein, carthame dyes (such as carthamin, for example), flavonoids (with morin, apigenidin, santal, for example), anthocyans (of the apigeninidin type), carotenoids, tannins, sorghum, and cochineal carmine, or mixtures thereof.

It is also possible to use extracts or decoctions containing natural dyes, in particular henna-based extracts.

Preferably, the natural dye or dyes are selected from lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, laccaic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidin, chlorophyllin, sorghum, orceins, cochineal carmine, hematein, hematoxylin, braziline, and brazilein, and mixtures thereof.

These dyes may optionally be used in the presence of mordants (for example salts of zinc, manganese, aluminum, iron etc.).

Reducing Agents

The composition may contain at least one reducing agent capable of reducing disulfide bonds in the hair.

It is possible to use a reducing agent of the phosphine or sulfite or alkaline bisulfite type. Advantageously, a thiol reducing agent is used.

Preferably, the thiol or thiols used as reducing agents in the reducing composition are selected from aminothiols such as cysteine and its derivatives, such as N-acetylcysteine, cysteamine and its derivatives, preferably its C₁-C₄ acylated derivatives such as N-acetyl cysteamine and N-propionyl cysteamine, and non-amino-containing thiols such as thiolactic acid and its esters, such as glycerol monothiolactate, thioglycolic acid and its esters, such as glycerol or glycol monothioglycolate, and thioglycerol.

When the thiol has at least one carboxylic acid function, if appropriate it is possible to use said thiol in the form of one or more of its salts, such as alkali metal or ammonium salts. It is thus possible to use thioglycolate ammonium as the thiol. If the thiol has an amino group, it would be possible to use said thiol in the form of one or more of its salts such as aminothiol halides. Thus, the thiol used in the context of the present invention may be L-cysteine hydrochloride.

Aminothiols that may be used in the reducing composition used in accordance with the invention and that may also be mentioned are N-mercapto-alkylamides of sugars, such as N-(mercapto-2-ethyl)gluconamide, pantheteine, N-(mercaptoalkyl)ω-hydroxyalkylamides such as those described in patent application EP-A-354 835 and N-mono- or N,N-dialkylmercapto 4-butyramides such as those described in patent application EP-A-368 763, aminomercaptoalkylamides such as those described in patent application EP-A-432 000 and alkylaminomercapto alkylamides such as those described in patent application EP-A-514 282. Examples of non-aminated thiols used in the invention that may also be mentioned are 2-hydroxypropyl thioglycolate (2/3) and 2-hydroxy-1-methylethyl thioglycolate (67/33) described in patent application FR-A-2 679 448, β-mercaptopropionic acid and its derivatives, and thiomalic acid.

It is possible to use a thiol-containing reducing agent, in particular thioglycolic acid or cysteine.

Organic or Inorganic Bases

For straightening, it is also possible to use strong bases such as alkali or alkaline-earth metal hydroxides, transition metal hydroxides or organic hydroxides. By way of example, examples of hydroxides that may be mentioned are sodium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide, strontium hydroxide, manganese hydroxide, zinc hydroxide, and guanidinium hydroxide. Preferred hydroxides are sodium hydroxide, calcium hydroxide, lithium hydroxide and guanidinium hydroxide.

Conditioning Agents

The conditioning agent may be selected from the group comprising non-silicone cationic polymers, non-silicone cationic surfactants, silicones, in particular organosiloxanes, linear or branched C₈-C₃₀ hydrocarbons, linear or branched C₈-C₃₀ fatty alcohols, esters of C₈-C₃₀ fatty acids and C₁-C₃₀ monoalcohols or polyols including esters of C₈-C₃₀ fatty acids and C₈-C₃₀ fatty alcohols, esters of C₁-C₇ acids or dibasic acids and C₈-C₃₀ fatty alcohols, ceramides or ceramide analogs, and mixtures of these compounds.

The term “cationic non-silicone polymer” means a polymer having no silicon atoms in its structure, charged positively when it is contained in the composition of the invention. This polymer may carry one or more permanent positive charges or contain one or more cationizable functions in the composition of the invention.

The cationic polymer or polymers that may be used as conditioning agents of the present invention are preferably selected from polymers comprising primary, secondary, tertiary, and/or quaternary groups forming part of the polymer chain or directly bonded thereto, and having a molecular weight (MW) in the range 500 to approximately 5,000,000, preferably in the range 1000 to 3,000,000.

When the conditioning agent is a cationic polymer, it is preferably selected from those containing motifs comprising primary, secondary, tertiary, and/or quaternary amine groups that may either form part of the main polymer chain or be carried by a lateral substituent bonded directly thereto.

More particular examples of cationic polymers that may be mentioned are polymers of the polyamine, polyaminoamide, and quaternary polyammonium type. These are known products. They are described, for example, in French patents numbers 2 505 348 and 2 542 997.

Some of these polymers that may be mentioned are:

(1) homopolymers or copolymers derived from acrylic or methacrylic esters or amides and comprising at least one of the motifs with the following formulae:

in which:

-   -   R₃ and R₄, which may be identical or different, represent         hydrogen or an alkyl group containing 1 to 6 carbon atoms,         preferably methyl or ethyl;     -   R₅, which may be identical or different, designate a hydrogen         atom or a CH₃ radical;     -   A, which may be identical or different, represent a linear or         branched alkyl group containing 1 to 6 carbon atoms, preferably         2 or 3 carbon atoms or a hydroxyalkyl group containing 1 to 4         carbon atoms;     -   R₆, R₇, R₈, which may be identical or different, represent an         alkyl group containing 1 to 18 carbon atoms or a benzyl radical,         preferably an alkyl group containing 1 to 6 carbon atoms; and     -   X designates an anion derived from an organic or inorganic acid         such as a methosulfate anion or a halide such as chloride or         bromide.

The copolymers of family (1) may further contain one or more motifs deriving from co-monomers that may be selected from the family of acrylamides, methacrylamides, acrylamides, diacetone acrylamides, and acrylamides and methacrylamides substituted on the nitrogen with lower (C₁-C₄)alkyls, acrylic or methacrylic acids or their esters, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, and vinyl esters.

Thus, copolymers of family (1) that may be mentioned include:

-   -   copolymers of acrylamide and dimethylaminoethyl methacrylate         quaternized with dimethyl sulfate or with a dimethyl halide such         as that sold under the trade name HERCOFLOC by the supplier         HERCULES;     -   copolymers of acrylamide and methacryloyloxyethyltrimethyl         ammonium chloride described, for example, in patent application         EP-A-080 976 and sold under the trade name BINA QUAT P 100 by         the supplier CIBA GEIGY;     -   the copolymer of acrylamide and methacryloyloxyethyltrimethyl         ammonium methosulfate sold under the trade name RETEN by the         supplier HERCULES;     -   quaternized or non-quaternized         vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate         copolymers such as the products sold under the trade name         “GAFQUAT” by the supplier ISP such as, for example, “GAFQUAT         734” or “GAFQUAT 755”, or the products designated as “COPOLYMER         845, 958, and 937”. These polymers are described in detail in         French patents 2 077 143 and 2 393 573;     -   dimethyl amino ethyl         methacrylate/vinylcaprolactam/vinylpyrrolidone terpolymers such         as the product sold under the trade name GAFFIX VC 713 by the         supplier ISP;     -   vinylpyrrolidone/methacrylamidopropyl dimethylamine copolymers,         in particular as sold under the trade name STYLEZE CC 10 by ISP.     -   and vinylpyrrolidone/quaternized dimethylamino propyl         methacrylamide copolymers such as the product sold under the         trade name “GAFQUAT HS 100” by the supplier ISP; and     -   cross-linked polymers of         methacryloyloxy(C₁-C₄)alkyl(C₁-C₄)trialkyl ammonium salts such         as the polymers obtained by homopolymerization of         dimethylaminoethylmethacrylate quaternized by methyl chloride,         or by copolymerization of acrylamide with         dimethylaminoethylmethacrylate quaternized by methyl chloride,         the homo- or copolymerization being followed by cross-linking         with a compound containing an olefinically unsaturated bond, in         particular methylene bis-acrylamide. More particularly, an         acrylamide/methacryloyloxyethyl trimethylammonium chloride         cross-linked polymer (20/80 by weight) may be used in the form         of a dispersion containing 50% by weight of said copolymer in         mineral oil. This dispersion is sold under the name “SALCARE® SC         92” by the supplier CIBA. It is also possible to use a         cross-linked homopolymer of methacryloyloxyethyl         trimethylammonium chloride, for example in dispersion in mineral         oil or in a liquid ester. These dispersions are provided under         the names “SALCARE® SC 95” and “SALCARE® SC 96” by the supplier         CIBA;

(2) polymers constituted by piperazinyl motifs and divalent alkylene or hydroxyalkylene radicals with straight or branched chains, possibly interrupted by oxygen, sulfur or nitrogen atoms or aromatic or heterocyclic cycles as well as the oxidation and/or quaternization products of said polymers. Such polymers are in particular described in French patents 2 162 025 and 2 280 361;

(3) polyaminoamides that are soluble in water prepared, in particular, by polycondensation of an acid compound with a polyamine; these polyaminoamides may be cross-linked with an epihalohydrin, a diepoxide, a dianhydride, an unsaturated dianhydride, a bis-unsaturated derivative, a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, a bis-alkyl halide or an oligomer resulting from the reaction of a bifunctional compound that is reactive towards a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, a bis-alkyl halide, an epihalohydrin, a diepoxide or a bis-unsaturated derivative; the cross-linking agent is used in proportions of 0.025 to 0.35 moles per amine group of the polyaminoamide; these polyaminoamides may be alkylated or, if they comprise one or more tertiary amine functions, they may be quaternized. Such polymers are in particular described in French patents 2 252 840 and 2 368 508;

(4) derivatives of polyaminoamides resulting from condensation of polyalkylene polyamines with polycarboxylic acids followed by alkylation with functional agents. Examples that may be mentioned are adipic acid-dialkylaminohydroxyalkyldialkylene triamine polymers in which the alkyl radical contains 1 to 4 carbon atoms and preferably designates methyl, ethyl or propyl. Such polymers are described in particular in French patent 1 583 363;

More particular examples of these derivatives that may be mentioned are adipic acid/dimethylamino-hydroxypropyl/diethylene triamine polymers provided under the trade name “Cartaretine F, F4, or F8” by the supplier Sandoz.

(5) polymers obtained by reacting a polyalkylene polyamine comprising two primary amine groups and at least one secondary amine group with a dicarboxylic acid selected from diglycolic acid and saturated aliphatic dicarboxylic acids containing 3 to 8 carbon atoms. The molar ratio between the polyalkylene polyamine and the dicarboxylic acid is in the range 0.8:1 to 1.4; the resulting polyaminoamide is reacted with epichlorhydrin in a molar ratio of epichlorhydrin to the second amine group of the polyaminoamide in the range 0.5:1 to 1.8:1. Such polymers are described in particular in American patents U.S. Pat. No. 3,227,615 and U.S. Pat. No. 2,961,347;

Polymers of this type are in particular sold under the trade name “Hercosett 57” by the supplier Hercules Inc. or under the trade name “PD 170” or “Delsette 101” by the supplier Hercules for an adipic acid/epoxypropyl/diethylene-triamine copolymer.

(6) alkyl diallyl amine or dialkyl diallyl ammonium cyclopolymers such as homopolymers or copolymers comprising motifs with formulae (V) or (V) as the principal constituent of the chain:

in which formulae k and t equal 0 or 1, the sum k+t being equal to 1; R₁₂ designates a hydrogen atom or a methyl radical; R₁₀ and R₁₁, independently of each other, designate an alkyl group containing 1 to 6 carbon atoms, a hydroxyalkyl group in which the alkyl group preferably contains 1 to 5 carbon atoms, a lower (C₁-C₄)amidoalkyl group, or R₁₀ and R₁₁ may, together with the nitrogen atom to which they are attached, designate heterocyclic groups such as piperidinyl or morpholinyl; and Y— is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate, or phosphate. These polymers are in particular described in French patent 2 080 759 and in its certificate of addition 2 190 406;

-   -   R₁₀ and R₁₁, independently of each other, preferably designate         an alkyl group containing 1 to 4 carbon atoms and more         particularly 1 carbon atom;

More particular examples of polymers as defined above that may be mentioned are the dimethyldiallyl ammonium chloride homopolymer sold under the trade name “Merquat 100” by the supplier NALCO (and its homologs with low mass average molecular weights) and copolymers of diallyldimethylammonium chloride and acrylamide sold under the trade name “MERQUAT 550”.

(7) the quaternary diammonium polymer containing recurring motifs with formula:

in which formula (VII):

-   -   R₁₃, R₁₄, R₁₅, and R₁₆, which may be identical or different,         represent aliphatic, alicyclic, or arylaliphatic radicals         containing 1 to 20 carbon atoms or lower hydroxyalkylaliphatic         radicals, or R₁₃, R₁₄, R₁₅ and R₁₆, together or separately,         constitute, together with the nitrogen atoms to which they are         attached, heterocycles optionally containing a second heteroatom         other than nitrogen or R₁₃, R₁₄, R₁₅ and R₁₆ represent a linear         or branched C₁-C₆ alkyl radical substituted with a nitrile,         ester, acyl, amide or —CO—O—R₁₇-D or —CO—NH—R₁₇-D group where         R₁₇ is an alkylene and D is a quaternary ammonium group;     -   A₁ and B₁ represent polymethylene groups containing 2 to 20         carbon atoms that may be linear or branched, saturated or         unsaturated, and may contain, linked to or interposed in the         main chain, one or more aromatic rings, one or more oxygen or         sulfur atoms or sulfoxide, sulfone, disulfide, amino,         alkylamino, hydroxyl, quaternary ammonium, ureido, amide or         ester groups; and     -   X⁻ designates an anion derived from an organic or inorganic         acid;     -   A₁, R₁₃, and R₁₅ may, with the two nitrogen atoms to which they         are attached, form a piperazine cycle; further, if A₁ designates         a linear or branched, saturated or unsaturated alkylene or         hydroxyalkylene radical, B₁ may also designate a group         (CH₂)_(n)—CO-D-OC—(CH₂)_(p)—; where n and p are integers in the         range approximately 2 to 20; and     -   D designates:

a) a glycol residue with formula: —O—Z—O—, where Z designates a linear or branched hydrocarbon radical or a group having one of the following formulae:

(CH₂—CH₂—O)_(x)—CH₂—CH₂—

[CH₂—CH(CH₃)—O]_(y)—CH₂—CH(CH₃)—

where x and y designate an integer in the range 1 to 4, representing a predetermined, unique degree of polymerization or any nucleic from 1 to 4 representing a mean degree of polymerization;

b) a bis-secondary diamine residue such as a piperazine derivative;

c) a bis-primary diamine residue with formula: —NH—Y—NH—, where Y designates a linear or branched hydrocarbon radical, or the bivalent radical

CH₂—CH₂—S—S—CH₂—CH₂—;

d) a ureylene group with formula: —NH—CO—NH—; and

X⁻ is preferably an anion such as chloride or bromide.

These polymers have a number average molecular mass that is generally in the range 1000 to 100,000.

Polymers of this type are described in particular in French patents 2 320 330, 2 270 846, 2 316 271, 2 336 434, and 2 413 907, and in U.S. Pat. Nos. 2,273,780, 2,375,853, 2,388,614, 2,454,547, 3,206,462, 2,261,002, 2,271,378, 3,874,870, 4,001,432, 3,929,990, 3,966,904, 4,005,193, 4,025,617, 4,025,627, 4,025,653, 4,026,945, and 4,027,020.

More particularly, polymers constituted by recurring motifs with the following formula may be used:

in which R₁₈, R₁₉, R₂₀ and R₂₁, which may be identical or different, designate an alkyl or hydroxyalkyl radical containing approximately 1 to 4 carbon atoms, r and s are integers in the range approximately 2 to 20 and, X⁻ is an anion derived from an organic or inorganic acid.

A particularly preferred compound with formula (VIII) is that in which R₁₈, R₁₉, R₂₀ and R₂₁, represent a methyl radical and r=3, s=6 and X═Cl, known as Hexadimethrine chloride using the INCI nomenclature (CTFA).

(8) quaternary polyammonium polymers constituted by motifs with formula (IX):

in which formula:

-   -   R₂₂, R₂₀, R₂₄ and R₂₅, which may be identical or different,         represent a hydrogen atom or a methyl, ethyl, propyl,         β-hydroxyethyl, β-hydroxypropyl or —CH₂CH₂(OCH₂CH₂)_(p)OH         radical;         where:     -   p is equal to 0 or to an integer in the range 1 to 6, provided         that R₂₂, R₂₀, R₂₄, and R₂₅ do not simultaneously represent a         hydrogen atom;     -   t and u, which may be identical or different, are integers in         the range 1 to 6;     -   v is equal to 0 or an integer in the range 1 to 34;     -   X⁻ designates an anion such as a halide;     -   A designates a radical of a dihalide or, preferably, represents         —CH₂—CH₂—O—CH₂—CH₂—.

Such compounds are described in particular in patent application EP-A-122 324.

Examples of the above that may be mentioned include the products “Mirapol® A 15”, “Mirapol® AD1”, “Mirapol® AZ1” and “Mirapol® 175” provided by the supplier Miranol;

(9) Quaternary vinylpyrrolidone and vinylimidazole polymers such as the products provided under the trade names Luviquat® FC 905, FC 550, and FC 370 by the supplier B.A.S.F, for example;

(10) Cationic polysaccharides, in particular celluloses and cationic galactomannan gums.

More particular examples of cationic polysaccharides that may be mentioned are derivatives of cellulose ethers comprising quaternary ammonium groups, cationic copolymers of cellulose or cellulose derivatives grafted with a hydrosoluble quaternary ammonium monomer and cationic galactomannan gums.

Derivatives of cellulose ethers comprising quaternary ammonium groups have been described in French patent 1 492 597. These polymers are also defined in the CTFA dictionary as quaternary ammonium hydroxyethylcellulose compounds that have reacted with an epoxide substituted with a trimethylammonium group.

Cationic cellulose copolymers or cellulose derivatives grafted with a hydrosoluble quaternary ammonium monomer are described in particular in the patent U.S. Pat. No. 4,131,576, such as hydroxyalkyl celluloses, for example hydroxymethyl-, hydroxyethyl- or hydroxypropyl-celluloses grafted in particular with a methacryloylethyl trimethylammonium salt, methacrylamidopropyl trimethylammonium salt, or dimethyl-diallylammonium salt.

Cationic galactomannan gums are described more particularly in patents U.S. Pat. Nos. 3,589,578 and 4,031,307, in particular guar gums containing cationic trialkylammonium groups. As an example, guar gums modified by a salt (for example chloride) of 2,3-epoxypropyl trimethylammonium may be used.

Other cationic polymers that may be used in the context of the invention are cationic proteins or cationic protein hydrolysates, polyalkyleneimines, in particular polyethyleneimines, polymers containing vinylpyridine or vinylpyridinium motifs, condensates of polyamines and epichlorhydrin, quaternary polyureylenes, and chitin derivatives.

Particular examples of cationic proteins or protein hydrolysates are chemically modified polypeptides carrying quaternary ammonium groups at the chain end or grafted thereto. Their molecular mass may, for example, be from 1500 to 10,000, in particular from approximately 2000 to 5000. Particular examples of these compounds that may be mentioned are as follows:

Preferably, these polypeptides are of vegetable origin.

The following may in particular be mentioned:

-   -   hydrolysates of wheat, soya, or rice protein modified by         cocodimonium hydroxypropyl groups;     -   hydrolysates of protein, soya, jojoba, oats, or rice wheat         modified by hydroxypropyl trimonium groups;     -   hydrolysates of wheat, soya, or jojoba protein modified by         laurdimonium hydroxypropyl groups; and     -   hydrolysates of jojoba, soya, or rice protein modified by         steardimonium hydroxypropyl groups.

Examples of these products that may be mentioned include the products provided by the supplier COGNIS under the trade name GLUADIN WQ, by the supplier CRODA under the trade names HYDROTRITICUM WQ PE or CROQUAT SOYA.

Preferred examples of cationic polymers that could be used in the context of the present invention are cationic cyclopolymers, in particular homopolymers or copolymers of dimethyldiallylammonium chloride, sold under the trade names “MERQUAT 100”, “MERQUAT 550” and “MERQUAT S” by the supplier NALCO, quaternary vinylpyrrolidone and vinylimidazole polymers and cationic polysaccharides, and mixtures thereof.

Non-Silicone Cationic Surfactants

The conditioning agent or agents that may be used in accordance with the invention may be selected from non-silicone cationic surfactants.

The term “non-silicone cationic surfactant” means a surfactant having no silicon atoms in its structure and positively charged when it is contained in the composition of the invention. This surfactant may carry one or more permanent positive charges or contain one or more cationizable functions in the composition of the invention.

The cationic surfactant or surfactants suitable for use as conditioning agents in the context of the present invention are preferably selected from primary, secondary, or tertiary fatty amines, possibly polyoxyalkylenated, or their salts, quaternary ammonium salts, and mixtures thereof.

The fatty amines generally comprise at least one C₈-C₃₀ hydrocarbon chain. Examples of fatty amines that may be used in accordance with the invention that may be mentioned are stearyl amidopropyl dimethylamine and distearylamine.

Examples of quaternary ammonium salts that may in particular be mentioned are as follows:

-   -   those with the following general formula (XII):

(XII) in which the radicals R₈ to R₁₁, which may be identical or different, represent a linear or branched aliphatic radical containing 1 to 30 carbon atoms or an aromatic radical such as aryl or alkylaryl, at least one of radicals R₈ to R₁₁ designating a radical containing 8 to 30 carbon atoms, preferably 12 to 24 carbon atoms. The aliphatic radicals may comprise heteroatoms such as oxygen, nitrogen, sulfur or the halogens. Examples of aliphatic radicals are selected from C₁-C₃₀ alkyl, C₁-C₃₀ alkoxy, (C₂-C₆)polyoxyalkylene, C₁-C₃₀ alkylamide, (C₁₂-C₂₂)alkyl(C₂-C₆)amidoalkyl, (C₁₂-C₂₂)alkyl acetate, and C₁-C₃₀ hydroxyalkyl; X⁻ is an anion selected from the group formed by halides, phosphates, acetates, lactates, (C₂-C₆)alkyl sulfates, and alkyl- or alkylaryl-sulfonates.

Preferred examples of quaternary ammonium salts with formula (XII) are tetraalkylammonium chlorides such as, for example, dialkyldimethylammonium or alkyltrimethylammonium chlorides in which the alkyl radical comprises approximately 12 to 22 carbon atoms, in particular behenyltrimethylammonium, distearyldimethylammonium, cetyltrimethylammonium, benzyldimethylstearylammonium chlorides or, alternateively, palmitylamidopropyltrimethylammonium chloride or stearamidopropyldimethyl-(myristyl acetate)-ammonium chloride such that sold under the trade name CERAPHYL® 70 by the supplier VAN DYK;

-   -   quaternary ammonium salts of imidazoline such as, for example,         those with the following formula (XIII):

in which R₁₂ represents an alkenyl or alkyl radical containing 8 to 30 carbon atoms, for example fatty acid derivatives from tallow, R₁₃ represents a hydrogen atom, a C₁-C₄ alkyl radical or an alkenyl or alkyl radical containing 8 to 30 carbon atoms, R₁₄ represents a C₁-C₄ alkyl radical, R₁₅ represents a hydrogen atom, a C₁-C₄ alkyl radical, X⁻ is an anion selected from the group formed by halides, phosphates, acetates, lactates, alkylsulfates, alkyl- or alkylaryl-sulfonates. Preferably, R₁₂ and R₁₃ designate a mixture of alkenyl or alkyl radicals containing 12 to 21 carbon atoms, for example fatty acid derivatives from tallow, R₁₄ designates a methyl radical, R₁₅ designates a hydrogen atom. An example of such a product is that sold under the trade name REWOQUAT® W 75 by the supplier REWO;

-   -   quaternary di- or triammonium salts, in particular with formula         (XIV):

in which R₁₆ designates an alkyl radical containing approximately 16 to 30 carbon atoms optionally hydroxylated and/or interrupted by one or more oxygen atoms, R₁₇ is selected from hydrogen or an alkyl radical containing 1 to 4 carbon atoms or a (R_(16a))(R_(17a))(R_(18a))N—(CH₂)₃— group, R_(16a), R_(17a), R_(18a), R₁₈, R₁₉, R₂₀, and R₂₁, which may be identical or different, being selected from hydrogen or an alkyl radical containing 1 to 4 carbon atoms, and X⁻ is an anion selected from the group formed by halides, acetates, phosphates, nitrates and methylsulfates. Examples of such compounds are Finquat CT-P promoted by the supplier FINETEX (Quaternium 89), Finquat CT promoted by the supplier FINETEX (Quaternium 75);

-   -   quaternary ammonium salts containing at least one ester         function, such as those with the following formula (XV):

in which:

-   -   R₂₂ is selected from C₁-C₆ alkyl radicals and C₁-C₆ hydroxyalkyl         or dihydroxyalkyl radicals;     -   R₂₃ is selected from:         -   the radical

-   -   -   radicals R₂₇, which are linear or branched, saturated or             unsaturated C₁-C₂₂ hydrocarbon radicals;         -   the hydrogen atom;

    -   R₂₅ is selected from:         -   the radical

-   -   -   radicals R₂₉, which are linear or branched, saturated or             unsaturated C₁-C₆ hydrocarbon radicals;         -   the hydrogen atom;

    -   R₂₄, R₂₆, and R₂₈, which may be identical or different, are         selected from linear or branched, saturated or unsaturated         C₇-C₂₁ hydrocarbon radicals;

    -   r, s, and t, which may be identical or different, are integers         from 2 to 6;

    -   y is an integer from 1 to 10;

    -   x and z, which may be identical or different, are integers from         0 to 10;

    -   X⁻ is a simple or complex organic or inorganic anion;

    -   provided that the sum x+y+z is equal to 1 to 15, that when x is         equal to 0 then R₂₃ designates R₂₇ and that when z is equal to 0         then R₂₅ designates R₂₉.

The R₂₂ alkyl radicals may be linear or branched, more particularly linear.

Preferably, R₂₂ designates a methyl, ethyl, hydroxyethyl, or dihydroxypropyl radical, and more particularly a methyl or ethyl radical.

Advantageously, the sum x+y+z is equal to a value in the range 1 to 10.

When R₂₃ is a hydrocarbon radical R₂₇, it may be long and contain 12 to 22 carbon atoms, or short and contain 1 to 3 carbon atoms.

When R₂₅ is a hydrocarbon radical R₂₉, it preferably contains 1 to 3 carbon atoms.

Advantageously, R₂₄, R₂₆, and R₂₈, which may be identical or different, are selected from linear or branched, saturated, or unsaturated C₁₁-C₂₁ hydrocarbon radicals, and more particularly from linear or branched, saturated or unsaturated alkyl and alkenyl C₁₁-C₂₁ radicals.

Preferably, x and z, which may be identical or different, are equal to 0 or 1.

Advantageously, y is equal to 1.

Preferably, r, s and t, which may be identical or different, are equal to 2 or 3, still more particularly equal to 2.

The anion X⁻ is preferably a halide (chloride, bromide or iodide) or an alkylsulfate, more particularly methylsulfate. However, it is possible to use the methanesulfonate, phosphate, nitrate, tosylate, an anion derived from an organic acid such as the acetate or lactate, or any other anion compatible with the ammonium possessing an ester function.

Still more particularly, the anion X⁻ is the chloride or the methylsulfate.

More particularly, in the composition of the invention, ammonium salts with formula (XV) are used in which:

-   -   R₂₂ designates a methyl or ethyl radical;     -   x and y are equal to 1;     -   z is equal to 0 or 1;     -   r, s and t are equal to 2;     -   R₂₃ is selected from:         -   the radical

-   -   -   methyl, ethyl, or C₁₄-C₂₂ hydrocarbon radicals;         -   the hydrogen atom;         -   R₂₅ is selected from:         -   the radical

-   -   -   the hydrogen atom;         -   R₂₄, R₂₆, and R₂₈, which may be identical or different, are             selected from linear or branched, saturated or unsaturated             C₁₃-C₁₇ hydrocarbon radicals, and preferably from linear or             branched, saturated or unsaturated C₁₃-C₁₇ alkyl and alkenyl             radicals.

Advantageously, the hydrocarbon radicals are linear.

Examples that may be mentioned are compounds with formula (XV) such as salts (in particular chloride or methylsulfate) of diacyloxyethyl-dimethylammonium, of diacyloxyethyl-hydroxyethyl-methylammonium, of monoacyloxyethyl-dihydroxyethyl-methylammonium, of triacyloxyethyl-methylammonium, or of monoacyloxyethyl-hydroxyethyl-dimethylammonium, and mixtures thereof. The acyl radicals preferably contain 14 to 18 carbon atoms and more particularly originate from a vegetable oil such as palm oil or sunflower oil. When the compound contains several acyl radicals, they may be identical or different.

Said products are obtained, for example, by direct esterification of triethanolamine, of triisopropanolamine, of alkyldiethanolamine, or of alkyldiisopropanolamine optionally oxyalkylenated on C₁₀-C₃₀ fatty acids or on C₁₀-C₃₀ fatty acid mixtures of animal or vegetable origin, or by transesterification of their methyl esters. This esterification is followed by quaternization using an alkylation agent such as an alkyl halide (preferably methyl or ethyl), a dialkyl sulfate (preferably methyl or ethyl), methyl methanesulfonate, methyl para-toluenesulfonate, or glycol, or glycerol chlorhydrin.

By way of example, such compounds are sold under the trade names DEHYQUART® by the supplier HENKEL, STEPANQUAT® by the supplier STEPAN, NOXAMIUM® by the supplier CECA, or REWOQUAT® WE 18 by the supplier REWO-WITCO.

The composition of the invention may, for example, contain a mixture of quaternary ammonium mono-, di- and trimester salts with a majority by weight of diester salts.

It is also possible to use ammonium salts containing at least one ester function as described in U.S. Pat. No. 4,874,554 and U.S. Pat. No. 4,137,180.

Particularly preferred cationic surfactant(s) that may be used in the invention are selected from compounds with formula (XII) or with formula (XV).

Preferred examples of cationic surfactants that may be present in the composition of the invention include cetyl trimethyl ammonium, behenyl trimethyl ammonium, dipalmitoylethyl hydroxyethyl methyl ammonium, distearoylethyl hydroxyethyl methyl ammonium, methyl(C₉-C₁₉)alkyl, (C₁₀-C₂₀)alkyl amidoethylimidazolium, and stearamidopropyldimethylamine salts, a salt of stearamidopropyl dimethylammonium, and mixtures thereof.

Silicones

Non-limiting examples of silicones that may be used as conditioning agents of the present invention that may be mentioned are:

I. Volatile Silicones:

These have a boiling point in the range 60° C. to 260° C. This type of silicone includes:

(i) cyclic silicones containing 3 to 7 silicon atoms, and preferably 4 to 5.

It may, for example, be the octamethylcyclo-tetrasiloxane sold under the name “VOLATILE SILICONE 7207®” by the supplier UNION CARBIDE or “SILBIONE 70045 V2®” by the supplier RHONE POULENC, the decamethylcyclopentasiloxane sold under the name “VOLATILE SILICONE 7158®” by the supplier UNION CARBIDE, “SILBIONE 70045 V5®” by the supplier RHONE POULENC, and also their mixtures. Cyclopolymers of the dimethylsiloxane/methylalkylsiloxane type, such as “SILICONE VOLATILE FZ 3109®” sold by the supplier UNION CARBIDE, which is a dimethylsiloxane/methyloctylsiloxane cyclocopolymer, may also be mentioned;

(ii) linear volatile silicones containing 2 to 9 silicon atoms and having a viscosity of 5×10⁻⁶ m²/s [square meters per second] or less at 25° C.

It may, for example, be the hexamethyldisiloxane sold under the trade name “SILBIONE 70041 V0,65®” by the supplier RHONE POULENC. This type of product is described in the article by TODD & BYERS, “Volatile silicone fluids for cosmetics”, Cosmetics and Toiletries, Vol. 91, January 76, pp. 27-32.

II. Non-Volatile Silicones

These are principally constituted by polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes and organomodified polysiloxanes, and also their mixtures. They may be in the form of oils, gums or resins.

Examples of polyalkylsiloxanes that may be mentioned are principally linear polydimethylsiloxanes with a viscosity of more than 5×10⁻⁶ m²/s, and preferably less than 2.6 m²/s, i.e.:

-   -   with terminal trimethylsilyl groups, non-limiting examples of         which are “SILBIONE®” oils from the 70047 series sold by the         supplier RHONE POULENC, Wacker Belsil DM 60000 oil from WACKER,         or certain “VISCASIL®” liquids from the supplier GENERAL         ELECTRIC;     -   with terminal trihydroxysilyl groups, such as oils from the “48         V®” series from the supplier RHONE POULENC.

In this class of polyalkylsiloxanes, mention can also be made of polyalkylsiloxanes provided by the supplier GOLDSCHMIDT under the trade names “ABILWAX 9800®” and “ABILWAX 9801®”, which are poly(C₁-C₂₀)alkylsiloxanes.

Examples of polyalkylarylsiloxanes that may be mentioned are polydimethylphenylsiloxanes, linear and/or branched polydimethyldiphenylsiloxanes with a viscosity of 10⁻⁵ to 5×10⁻² m²/s such as, for example:

-   -   “RHODORSIL®” oil 763 from RHONE POULENC;     -   “SILBIONE®” oils from the 70641 series from RHONE POULENC, such         as “SILBIONE 70641 V30®” and “SILBIONE 70641 V200®” oils;     -   the product “DC 556®” Cosmetic Grad Fluid from DOW CORNING;     -   silicones from the series PK de BAYER, such as “PK20®”;     -   silicones from the series PN, PH de BAYER, such as “PN 1000®”         and “PH 1000®”; and     -   certain oils from the SF series from GENERAL ELECTRIC, such as         “SF 1250®”, “SF 1265®”, “SF 1154®”, “SF 1023®”.

The silicone gums of the present invention are polydiorganosiloxanes with a high number average molecular mass in the range 200,000 to 1,000,000, used alone or as a mixture in a solvent selected from volatile silicones, polydimethylsiloxane oils (PDMS), polyphenylmethylsiloxanes (PPMS) oils, isoparaffins, methylene chloride, pentane, dodecane, tridecane, tetradecane, or mixtures thereof.

Examples that may be mentioned are compounds containing the following structures:

-   -   poly[(dimethylsiloxane)/(methylvinylsiloxane)]gums;     -   poly[(dimethylsiloxane)/(diphenylsiloxane)] gums;     -   poly[(dihydrogeno dimethylsiloxane)/(divinylsiloxane)] gums;     -   poly[(dimethylsiloxane)/(phenylmethylsiloxane)] gums;     -   poly[(dimethylsiloxane)/(diphenylsiloxane)/(methylvinylsiloxane)]         gums.

Mirasil DM 300 000 from Rhodia may be mentioned.

The following non-limiting examples may also be mentioned:

1) mixtures formed from a polydimethylsiloxane hydroxylated at the chain end (DIMETHICONOL in the CTFA nomenclature), and a cyclic polydimethylsiloxane (CYCLOMETHICONE in the CTFA nomenclature), such as the products “Q2 1401®” or DOW CORNING 1501 FLUID provided by the supplier DOW CORNING;

2) mixtures formed from a polydimethylsiloxane gum with a cyclic silicone, such as the product “SF 1214 SILICONE FLUID®” from GENERAL ELECTRIC, which is a “SE 30 ®” gum with a MW of 500000 (number average) dissolved in “SF 1202 SILICONE FLUID®” (decamethylcyclopentasiloxane);

3) mixtures of two PDMS with different viscosities, in particular a PDMS gum and a PDMS oil, such as the products “SF 1236®” and “CF 1241®” from the supplier GENERAL ELECTRIC. The product “SF 1236®” is a mixture of a “SE 30®” gum as defined above with a viscosity of 20 m²/s and a “SF 96®” oil with a viscosity of 5×10⁶ m²/s (15% of “SE 30®” gum and 85% of “SF 96®” oil).

The product “CF 1241®” is a mixture of a “SE 30®” (33%) gum and a PDMS (67%) with a viscosity of 10⁻³ m²/s.

The organopolysiloxane resins that may be used in accordance with the invention are cross-linked siloxane systems comprising the units: R₂SiO₂/2, RSiO₃/2 and SiO₄/2 in which R represents a hydrocarbon group containing 1 to 6 carbon atoms or a phenyl group. Particularly preferred examples of these products are those in which R designates a lower alkyl radical or a phenyl radical.

Examples of these resins that may be mentioned are the product sold under the trade name “DOW CORNING 593®” or those sold under the trade names “SILICONE FLUID SS 4230” and “SILICONE FLUID SS 4267” by the supplier GENERAL ELECTRIC and that are dimethyl/trimethylpolysiloxanes.

The organomodified silicones of the present invention are silicones as defined above, comprising in their general structure one or more organo-functional groups bonded directly to the siloxane chain or bound via a hydrocarbon radical.

Examples that may be mentioned are silicones comprising:

a) perfluorinated groups such as trifluoroalkyls such as, for example, those provided by the supplier GENERAL ELECTRIC under the trade names “FF.150 FLUOROSILICONE FLUID®” or by the supplier SHIN ETSU under the trade names “X-22-819®”, “X-22-82®”, “X-22-821®” and “X-22-822®”;

b) hydroxyacylamino groups such as, for example, those described in patent application EP 0 342 834 and in particular the silicone sold by the supplier DOW CORNING under the trade name “Q2-8413®”;

c) thiol groups such as in the silicones “X 2-8360®” from the supplier DOW CORNING or “GP 72A®” and “GP 71®” from GENESEE;

d) non-quaternized amino groups, such as in “GP 4 SILICONE FLUID®” from GENESEE, “GP 7100®” from GENESEE, “Q2 8220®” from DOW CORNING, “AFL 40®” from UNION CARBIDE or the silicone known as “Amodimethicone” in the CTFA dictionary;

e) carboxylate groups, such as the products described in patent EP 186 507 from CHISSO CORPORATION;

f) hydroxyl groups such as polyorganosiloxanes with a C₂-C₁₈ hydroxyalkyl function described, for example, in patent application FR 85/16334; more particularly mention may be made of the product supplied by Dow Corning under the name DC 190;

g) alkoxy groups such as those in the silicone copolymer “F 755®” from SWS SILICONES and the products “ABILWAX 2428®”, “ABILWAX 2434®”, “ABILWAX 2440®” from the supplier GOLDSCHMIDT;

h) (C₈-C₂₂) acyloxy(C₂-C₁₈)alkyl groups such as the polyorganopolysiloxanes described in patent application FR 88/17433, for example;

i) quaternary ammonium groups such as in the products “X2 81 08®” and “X2 81 09®”, the product “ABIL K 3270®” from the supplier GOLDSCHMIDT;

j) amphoteric or betaine groups, such as those in the product provided by the supplier GOLDSCHMIDT under the trade name “ABIL B 9950®”;

k) bisulfite groups such as in the products provided by the supplier GOLDSCHMIDT under the trade names “ABIL S 201®” and “ABIL S 255®”; and

l) polyethyleneoxy and/or polypropyleneoxy groups optionally comprising C₆-C₂₄ alkyl groups, such as products known as dimethicone copolyol provided by the supplier DOW CORNING under the trade name DC 1248 or SILWET L 722, L 7500, L 77, L 711 oils from the supplier UNION CARBIDE and the (C₁₂)alkyl methicone copolyol provided by the supplier DOW CORNING under the trade name Q2 5200;

In accordance with the invention, it is also possible to use silicones comprising a polysiloxane portion and a portion constituted by an organic non-silicone chain, one of the two portions constituting the main chain of the polymer, the other being grafted onto said principal chain. These polymers are, for example, described in patent applications EP-A-412 704, EP-A-412 707, EP-A-640 105 and WO 95/00578, EP-A-582 152 and WO 93/23009 and in U.S. Pat. Nos. 4,693,935, 4,728,571, and 4,972,037. These polymers are preferably anionic or non-ionic.

Examples of such polymers are copolymers that can be obtained by radical polymerization from a mixture of monomers constituted by:

a) 50% to 90% by weight of tertiobutyl acrylate;

b) 0 to 40% by weight of acrylic acid;

c) 5% to 40% by weight of silicone macromer with formula:

with v being a number from 5 to 700; the percentages by weight are calculated relative to the total monomer weight.

Other particular examples of graft silicone polymers are polydimethylsiloxanes (PDMS) onto which mixed polymer motifs are grafted, via a linker of the thiopropylene type, which mixed polymer motifs are of the poly(meth)acrylic and alkyl poly(meth)acrylate types, and polydimethylsiloxanes (PDMS), onto which polymer motifs of the poly isobutyl(meth)acrylate type are grafted via a thiopropylene type linker.

In accordance with the invention, all of the silicones may also be used in the form of emulsions, nanoemulsions or microemulsions.

Particularly preferred polyorganosiloxanes of the invention are:

-   -   non-volatile silicones selected from the polydialkylsiloxane         family with terminal trimethylsilyl groups, such as oils with a         viscosity in the range 0.2 m²/s to 2.5 m²/s at 25° C., for         example oils from the DC200 series from DOW CORNING, in         particular that with a viscosity of 60,000 Cst, from the         SILBIONE 70047 series, more particularly 70,047 V 500,000 oil         provided by the supplier RHODIA CHIMIE, polydialkylsiloxanes         with terminal dimethylsilanol groups such as dimethiconol or         polyalkylarylsiloxanes such as SILBIONE 70641 V 200 oil provided         by the supplier RHODIA CHIMIE; and     -   polysiloxanes with amine groups such as aminodimethicones or         trimethylsilylamodimethicone.

The viscosities of the silicones may in particular be determined using the standard ASTM D445-97 (viscometry).

Hydrocarbons

When the conditioning agent of the composition of the invention is a hydrocarbon, it is a linear or branched C₈-C₃₀₀ hydrocarbon.

Particular examples of hydrocarbons that are liquid at ambient temperature that fall within this definition that can be mentioned are isododecane, isohexadecane and its isomers (such as 2,2,4,4,6,6-heptamethylnonane), isoeicosane, isotetracosane, isomers of said compounds, n-dodecane, n-nonane, n-undecane, n-tridecane, n-pentadecane, vaseline oil and mixtures of said hydrocarbons.

Preferably, vaseline oil, isododecane or one of its isomers is used in the invention.

Fatty Alcohols

When the conditioning agent is a fatty alcohol, it is of the linear or branched, saturated or unsaturated C₈-C₃₀ type. Examples of these that may be mentioned are 2-butyl octanol, lauric alcohol, oleic alcohol, isocetyl alcohol, isostearic alcohol, behenyl alcohol, stearyl alcohol, cetyl alcohol, and mixtures thereof.

Fatty Esters

When the conditioning agent is a fatty ester, it may either be an ester of a C₈-C₃₀ fatty acid and C₁-C₃₀ monoalcohols or polyols including esters of C₈-C₃₀ fatty acids and C₈-C₃₀ fatty alcohols, or an ester of a C₁-C₇ dibasic acid and a C₈-C₃₀ fatty alcohol.

Examples of such esters that may be mentioned are ethyl, isopropyl, 2-ethylhexyl and 2-octyldecyl palmitate, isopropyl, butyl, cetyl and 2-octyldecyl myristate, butyl and hexyl stearate, hexyl and 2-hexyldecyl laurate, isononyl isononanoate, dioctyl malate, dioctyl, myristyl myristate, stearyl myristate, cetyl palmitate, myristyl stearate, stearyl stearate, cetyl stearate, and mixtures thereof.

It is also possible to mention natural or synthetic triglycerides, in particular vegetable oils such as rapeseed oil, avocado oil, olive oil, sunflower oil, argan oil, or grapeseed oil.

Ceramides

Ceramides or ceramide analogs, such as glycoceramides, that can be used as a conditioning agent in the compositions of the invention are known per se and are natural or synthetic molecules that may have the following general formula (XIX):

in which:

-   -   R₁ designates a, linear or branched, saturated or unsaturated         alkyl radical derived from C₁₄-C₃₀ fatty acids, said radical         possibly being substituted with a hydroxyl group in the alpha         position, or a hydroxyl group in the omega position esterified         by a saturated or unsaturated C₁₆-C₃₀ fatty acid;     -   R₂ designates a hydrogen atom or a (glycosyl)_(n),         (galactosyl)_(m) or sulfogalactosyl radical, in which n is an         integer in the range 1 to 4 and m is an integer in the range 1         to 8; and     -   R₃ designates a C₁₅-C₂₆ hydrocarbon radical, saturated or         unsaturated in the alpha position, said radical possibly         substituted with one or more C₁-C₁₄ alkyl radicals;

it being understood that with natural ceramides or glycoceramides, R₃ may also designate a C₁₅-C₂₆ alpha-hydroxyalkyl radical, the hydroxyl group optionally being esterified by a C₁₆-C₃₀ alpha-hydroxyacid.

Ceramides that are preferred in the context of the present invention are those described by DOWNING in Arch. Dermatol, Vol. 123, 1381-1384, 1987, or those described in French patent FR 2 673 179.

A more particularly preferred ceramide or more particularly preferred ceramides of the invention are compounds for which R₁ designates a saturated or unsaturated alkyl derivative of C₁₆-C₂₂ fatty acids; R₂ designates a hydrogen atom; and R₃ designates a saturated C₁₅ linear radical.

Examples of such compounds are:

-   N-linoleoyldihydrosphingosine; -   N-oleoyldihydrosphingosine; -   N-palmitoyldihydrosphingosine; -   N-stearoyldihydrosphingosine; -   N-behenoyldihydrosphingosine; or

mixtures of these compounds.

Still more preferably, ceramides are used for which R₁ designates a saturated or unsaturated alkyl radical derived from fatty acids; R₂ designates a galactosyl or sulfogalactosyl radical; and R₃ designates a —CH═CH—(CH₂)₁₂—CH₃ group.

An example that may be mentioned is the product constituted by a mixture of these compounds, sold under the trade name GLYCOCER by the supplier WAITAKI INTERNATIONAL BIOSCIENCES.

Abrasive Solid Particles

The term “abrasive solid particles” means particles with a hardness that is greater than or equal to that of hair. As an example, the abrasive solid particles may have a hardness of 3 or more on the Mohs scale, or even 4 or more, for example 5 or more on the Mohs scale.

The solid particles may be selected from natural materials, in particular of mineral or vegetable origin, or from synthetic materials. The abrasive solid particles may, for example, be selected from the following materials, although this list is not limiting:

-   -   inorganic and/or metallic particles such as boron nitride in the         cubic form (Borazon®), aluminosilicate, zircon, mixed aluminum         oxides such as emery, zinc oxide, aluminum oxides such as         aluminas or corundum, titanium oxide, mica titanium oxide,         carbides, in particular silicon carbide (carborundum), or other         metallic oxides, metals and metal alloys such as iron shot,         steel, in particular pearlite; silicates such as glass, quartz         or sand, calcium carbonate (for example bora bora sand or Rose         de Brignoles marble) or magnesium carbonate, sodium chloride,         pumice stone, amorphous silica, diamond, or ceramics;     -   organic particles such as fruit kernels, especially apricot, for         example Scrubami® apricot, wood cellulose, for example ground         bamboo, coconut shell, for example Coconut exfoliator;         polyamides, in particular Nylon-6, sugars; polyethylenes;         polypropylenes; and     -   mixed particles combining organic and inorganic compounds, and         particles coated with the compounds described above.

The solid particles may have a flattened, spherical, elongate, polyhedral or irregular shape. The solid particles may, for example, originate from powdered pumice stone grains, powdered diamond, powdered fruit kernels, powdered coconut shells, microbeads, for example alumina microbeads, glass microbeads, polyamide microbeads, in particular Nylon-6, or from fibers, in particular polyamide fibers and hardwood cellulose fibers.

Moisturizing Agents

The moisturizing agents are preferably selected from urea, urea derivatives such as hydroxyethylurea, polyols such as glycerin, propyleneglycol or sorbitol, polyethylene glycols.

Preferably, the composition of the invention comprises at least one conditioning agent or at least one reducing agent or at least one organic or inorganic base, or at least one hair dye.

Still more preferably, the composition of the invention comprises at least one hair conditioning agent.

The cosmetic hair composition used in accordance with the invention may also contain other compounds that are normal in the hair cosmetics field, such as vitamins and pro-vitamins including panthenol, sunscreens, organic or inorganic pigments, which may optionally be colored, pearlizing and opacifying agents, sequestrating agents, plasticizers, solubilizing agents, anti-oxidants, hydroxyacids, fragrances, non-ionic, anionic, cationic or amphoteric surfactants, non-ionic, anionic, cationic or amphoteric polymers, short chain alkanols such as ethanol or isopropanol, acidifying agents and preservatives.

The compositions of the invention may be aqueous or anhydrous. They may be in the form of powders, liquids, gels, milks, creams or non-powdery solids. They may optionally be sprayed onto the hair using an aerosol or a pump bottle.

The method of the invention may be implemented in a plurality of variant embodiments.

In first variant exemplary embodiments, the hair is combed using a motor-driven device after applying the composition of the invention to the hair, the composition possibly being present on the hair.

In second variant exemplary embodiments, the hair is combed using a motor-driven device before applying the composition of the invention to the hair. In these variant exemplary embodiments, combing is carried out after wetting the hair or after applying a composition not comprising active ingredients of the invention.

The first variant exemplary embodiments are preferred. The method according to these variant exemplary embodiments may also include a subsequent step of applying of a composition with or without active ingredients of the invention.

The treatment may optionally be followed by rinsing.

Finally, the hair is dried or left to dry.

The method of the invention may be repeated several times. In general, the method of the invention is applied once or twice.

The invention is particularly suitable for curly or frizzy hair.

The invention can be better understood from the following description of non-limiting examples made with reference to the accompanying drawings in which:

FIG. 1 represents an example of a combing device of the invention;

FIG. 2 represents the device of FIG. 1 in diagrammatic section;

FIG. 3 diagrammatically illustrates the deformation of the diaphragm during operation of the device;

FIG. 4 illustrates the use of the device

FIG. 5 is a diagrammatic and perspective representation of a variant embodiment of a combing device; and

FIGS. 6A and 6B represent a head of hair respectively with one side treated in accordance with the invention and the other side treated conventionally.

The motor-driven combing device represented in FIGS. 1 and 2 comprise a hand piece 10 that can receive a detachable diaphragm 20 carrying spikes 21.

The combing device may be offered to the user with a charging unit 30 for recharging a battery 18 contained in the hand piece 10.

In the example illustrated, the device is similar to those promoted under the trade name NEO or FLEX by TWINBIRD and to that described in particular in patent application US 2009/0182249 A1; a section of it is reproduced in FIG. 2.

It can be seen in this figure that the hand piece comprises a geared electric motor 11 driving a drive member 12 in rotation on which is articulated a rod 13, connected to the diaphragm 20 by means, for example, of a hook 15 that is engaged in a portion in relief 22 provided on the inner face of the diaphragm 20.

Its periphery may be attached to a rim 16 of the casing of the hand piece 10.

In FIG. 2, it can be seen that a block 23 of an elastically, deformable, porous material forming a reservoir may be disposed on the inner face side of the diaphragm, but in a variant embodiment, this material is absent. Openings 25 may allow communication between the outside of the diaphragm 20, between the spikes 21, and the block 23.

As illustrated, the hand piece may include a switch 17 that can start the electric motor 11 that is powered via the battery 18.

The spikes 21 may have different heights, generally being shorter in the central region of the diaphragm and longer at its periphery, to provide the envelope surface touching the free ends of the spikes 21 with a generally concave shape.

As illustrated, the spikes 21 may be distributed into two groups, namely a first group 21 a disposed in the central region with spikes that are oriented parallel to the axis X of movement of the portion in relief, and a second group 21 b with spikes disposed about the first, the respective longitudinal axes of which extend obliquely outwardly relative to the axis X.

The spikes 21 may be disposed in concentric rows to the circumference of the diaphragm. Thus, the spikes 21 are not aligned and when the combing device is moved along a lock of hair in a direction perpendicular to or obliquely to its major axis Y, the hair that passes between the spikes 21 follows a non-rectilinear path.

During operation of the device, the rod 13 is driven in an oscillating motion from top to bottom in FIG. 2, which causes periodic deformation of the diaphragm 20, the periphery of the diaphragm 20 remaining fixed relative to the hand piece 10 while its central region oscillates along the axis X with a maximum amplitude.

As illustrated in FIG. 3, the oscillations of the diaphragm 20 generate a rubbing action of the spikes 21 on the hair that, combined with the use of the composition of the invention, can achieve results that are superior using the composition alone or the combing device alone.

To use the combing device, as illustrated in FIG. 4, the user may apply the composition to the wetted hair and comb the hair, for example by passing it a few times from the base to the tips.

EXAMPLE

The protocol was as follows:

a) applying a composition A comprising 1% active ingredient of a polydimethysiloxane, or B comprising 0.5% active ingredient of trimetylcetylammonium chloride to wetted hair, for example of the African or Caucasian type;

b) distribution of the composition using the hands and combing by hand or a comb on a first side of the head, and using the NEO device from the supplier TWINBIRD on the other side of the head, for 2 minutes;

c) rinsing; and

d) drying.

Applying the method, particularly to frizzy or curly hair in association with compositions A or B containing the active ingredient shows, as illustrated in FIGS. 6A and 6B, better individualization of the hair, resulting in a very clear reduction in volume and density compared with massage using the hands. Better disentangling and a smoother feel was also observed. This effect lasted through several shampooings.

Steps a) and b) could also be repeated after step c) then terminated by steps c) and d).

The scope of the invention also encompasses using a combing device comprising, as illustrated in FIG. 5, a removable reservoir 40 containing the composition to be applied during use of the combing device. The reservoir 40 is, for example, pre-filled with composition and is supplied to the operator in the form of a cartridge to be placed in the hand piece 10.

The composition from the reservoir is distributed, for example, by means of a pump actuated by the same motor as that which deforms the diaphragm.

The expression “comprising at least one” should be construed as being equivalent to “comprising one or more”. 

1. A method for treating hair, the method comprising: applying a composition to the hair, combing the hair using a motor-driven combing device, wherein the composition comprises at least one active ingredient selected from the group consisting of a hair conditioning agent, a reducing agent, an organic or inorganic base, a hair dye, an abrasive solid particle, and a moisturizing agent, and the motor-driven combing device comprises a flexible diaphragm carrying spikes in contact with the hair, and a drive mechanism enabling the flexible diaphragm to be deformed periodically to generate an oscillating movement of the spikes.
 2. The method according to claim 1, wherein the hair is combed by the motor-driven device after applying some of the composition to the hair.
 3. The method according to claim 1, wherein the hair is combed by the motor-driven device before applying some of the composition to the hair.
 4. The method according to claim 1, wherein a frequency of oscillation of the flexible diaphragm is from 0.5 Hz to 200 Hz.
 5. The method according to claim 1, wherein an envelope surface defined by free ends of the spikes is concave towards scalp with a radius of curvature that varies with deformations of the flexible diaphragm.
 6. The method according to claim 1, wherein a travel axis of the flexible diaphragm is perpendicular to scalp at least while combing base of hair.
 7. The method according to claim 1, wherein the spikes are made from a thermoplastic material.
 8. The method according to claim 1, wherein the composition comprises at least one hair dye selected from the group consisting of a synthetic direct dye, a natural dye, and an oxidation dye precursor.
 9. The method according to claim 1, wherein the composition comprises at least one reducing agent selected from the group consisting of phosphine, an alkaline sulfite, an alkaline bisulfite, and a thiol.
 10. The method according to claim 1, wherein the composition comprises at least one organic or inorganic base selected from the group consisting of an alkali or alkaline-earth hydroxide, a transition metal, and an organic hydroxide.
 11. The method according to claim 1, wherein the composition comprises at least one hair conditioning agent selected from the group consisting of a non-silicone cationic polymer, a non-silicone cationic surfactant, a silicone, a linear or branched C8-C30 hydrocarbon, a linear or branched C8-C30 fatty alcohol, an ester of a C8-C30 fatty acid and a C1-C30 mono-alcohol or polyol, a ceramide, and a ceramide analog.
 12. The method according to claim 1, wherein the composition comprises at least one abrasive solid particle selected from the group consisting of a natural material and a synthetic material.
 13. The method according to claim 1, wherein the composition comprises at least one moisturizing agent selected from the group consisting of a urea, a urea derivative, and a polyol.
 14. The method according to claim 1, wherein said combing lasts for a period of from 1 minute to 5 minutes.
 15. The method according to claim 1, wherein the active ingredient is more than 0.001% by weight relative to a total composition weight, the active ingredient is applied alone or with other ingredients, and when the active ingredient is applied with other ingredients, the active ingredient optionally is up to 50% of the total composition weight.
 16. The method according to claim 1, wherein the composition comprises an abrasive solid particle which is a natural material of mineral or vegetable origin. 